Fiber glass mat, method and laminate

ABSTRACT

A fiber glass mat containing a novolac resin having an acid solubility of at least about 35 wt. percent is especially useful for bonding to a light weight fibrous or foam web or board, such as a polymer fiber web. A method of making the mat by wet laying a slurry containing the fiber and the novolac resin particles and then further adding an aqueous solution or slurry containing a crosslinking agent for the novolac resin and a laminate containing the fiber glass mat are disclosed.

This application is a division of application Ser. No. 09/619,430, filedJul. 19, 2000, now U.S. Pat. No. 6,548,155.

The present invention involves mats having particular use in bonding tofibrous webs and boards and to foam boards for uses such as in makingautomotive parts like headliners or topliners, lightweight structuralparts, and other laminates. The present invention also involves a methodof making mats and laminates that contain one or more layers of theinventive mat. The mats produced according to this invention are usefulas reinforcement and dimensional stabilizers for making a large numberof inorganic, polymeric and/or natural fibrous web and foam laminateproducts.

BACKGROUND

It is known to use nonwoven fiber mats made with glass fibers and bondedwith aqueous thermosetting resins, like urea formaldehyde or phenolicresole resins to make molded parts and laminates. It is also known touse a nonwoven fiber glass mat to laminate to polymeric foam such aspolystyrene foam to act as stiffeners and stabilizers in the manufactureof automotive parts such as automobile head liners, as disclosed in U.S.Pat. No. 4,729,917. Products produced with foam laminates having one ortwo layers of nonwoven fiber glass mat with urea formaldehyde binder areaffected by high humidity and high ambient temperature to cause anunpleasant odor and also to deteriorate the binder strength. Also,non-extendible mat, i.e. a mat bound with a resin binder that is fullycured, is relatively stiff and does not conform well to curves andcomplex curvature, such as three dimensional curvature, and stillprovide excellent rigidity or stiffness to the foam laminate.

It is also known to make nonwoven fiber glass mats by chopping drystrands of glass fibers bound together with a binder to form choppedstrand, to collect the chopped strand on a moving conveyor in a randompattern, and to bond the chopped strand together at their crossings bydusting a dry, powdered thermoplastic binder like a polyamide, polyesteror ethylene vinyl acetate on wetted chopped strands followed by dryingand curing the binder, as disclosed in U.S. Pat. No. 5,565,049. Whilesuch mat products are very useful including bonding to a layer ofpolymeric foam to stiffen the foam, these mats do not have as high atensile strength as desired, and as achieved with a wet laid nonwovenfiber glass mat, because the bundles or chopped strands in the mat,according to the invention of the above cited patent, do not bondtogether as well as the individual fibers in a typical nonwoven mat.

For example, the average sum of the machine direction tensile and thecross machine direction tensile for a chopped fiber glass strand matmade in this manner and having a basis weight of about 1.88 pounds per100 sq. ft. is about 24 lbs. per 3 inch width compared to at least twicethis tensile for wet laid nonwoven fiber glass mats. Mats made accordingto the above patented process also are more expensive to make than atypical nonwoven mat made with known wet laid processes.

It is also known to make a nonwoven fiber glass mat bonded with “B”staged acrylic resin having a glass transition temperature above 45degrees C. and to use such mats to form a laminate with a foam layer foruse in automotive head liners as disclosed in U.S. Pat. No. 6,008,147,but this mat is not well suited for laminating to a polymeric fibrousweb when the desired shape contains complex curvatures requiring the matto stretch substantially during molding. Further, it is known to use anacrylic copolymer latex, such as a self-crosslinking acrylic copolymerof an anionic emulsifying type as one component of at least a twocomponent binder for bonding glass fibers and particulate thermoplasticto make a glass fiber reinforced sheet that can later be hot molded intovarious shapes and articles, as disclosed in U.S. Pat. No. 5,393,379.

Finally, it is known to make stampable, moldable, sheets of fiber glassreinforced thermoplastic by forming a dilute aqueous slurry containingglass fibers and thermoplastic particles or thermosetting particlessmaller than 1 millimeter in size and passing the slurry through amoving forming screen to form the sheet and drying the sheet at atemperature high enough to bond the plastic particles together whileretaining the particulate shape of the plastic particles, as disclosedin European Patent Specification 148,760. A conventional aqueous binderis applied to the wet formed mat of fibers and plastic particles when amat intended for cutting and press molding is made. The added aqueousbinder provides the strength in the dry mat needed to withstand handlingin the cutting and press molding operations.

European Patent Application 148,761 and U.S. Pat. No. 4,690,860 alsoteach similar methods and mats as taught by European PatentSpecification 148,760. U.S. Pat. No. 4,690,860 teaches inpregnating astampable sheet containing glass fibers and a thermoplastic binder witha liquid thermosetting plastics material like liquid phenol formaldehydeor liquid melamine formaldehyde resin and then molding the sheet atelevated temperature and pressure to form a molded product that retainsits hardness over a wider range of temperatures. This reference alsosuggests using powdered thermosetting resins like those used for in-moldcoating of known art, but does not suggest forming a fibrous non-wovencontaining a novolac resin bonding the crossing fibers togetherthroughout the mat. Sheets or mats made according to these disclosuresare not sufficiently rigid or heat and sag, resistant for certainapplications like automotive headliners because they contain a 40-60percent of thermoplastic material and do not have a thermosetting matrixthroughout the mat.

SUMMARY OF THE INVENTION

The present invention includes a fibrous nonwoven mat for laminating toother mats of the same or similar composition, to mats of differentcomposition and to various other materials such as wood, a polymericfiber web, fiber glass wool or mineral fiber webs or boards, foamboards, etc. comprising dispersed and crossing glass fibers boundtogether with a substantially melted Novolac resin having a solubilityin acetone of at least about 35 weight percent, preferably at leastabout 50% and most preferably at least about 70% to about 90 or 95percent such as about 85%, the Novolac resin preferably being a phenolicor epoxy Novolac resin. The mat also contains a crosslinking orhardening agent like hexamethylene tetramine. A Novalac resin as usedherein is a product of partially polymerized first stage phenol or epoxycontaining less than a stoichiometric amount of a crosslinking agentsuch as formaldehyde, amine, or other known crosslinking agent oragents. Novolac resins are well known in the art and normally areavailable as a powdered resin. Preferably the novolac resin is presentin the finished mat in amounts of 10-60 weight percent based on theweight of the dry mat, more preferably 45-55 wt. percent, and mostpreferably about 48-52 wt. percent. The novolac particles should be of asize range that allow all or most of the particles to become entrappedin the mat is the mat is being formed. When one inch long M glass fiberis used, the preferred particle size of the novolac is minus 40 mesh toplus 100 mesh (U.S. Std.).

The invention also includes a method of making the nonwoven matdescribed above comprising dispersing glass fibers and Novolac powder inan aqueous slurry, collecting the dispersed fibers onto a movingpermeable support to form a wet, fibrous, nonwoven mat, saturating thewet mat with an aqueous solution of slurry containing a crosslinking,hardening agent for the novolac resin, removing excess water andhardening agent from the wet, nonwoven mat and drying and heating themat in a temperature and time environment that will melt the Novolacpowder forming bonds where the fibers cross each other, but notthermoset the resulting Novolac resin bonds.

The present invention also includes molded laminates containing the matof the present invention on at least one surface of a polymeric,inorganic or natural fibrous web or board or foam core. The fibrous webpreferably can be a spun bonded, meltblown or a carded, lapped andneedled web of organic polymer or natural fiber.

The mats of the present invention preferably have bundles ofincompletely dispersed fibers in which the fibers are preferably atleast 0.75 inch long and most preferably at least 1 inch long. The matscan also contain pigments, dyes, flame retardants, and other additivesso long as they do not significantly reduce the ability of the mat tobond to a foam surface. The pigments or other additives can be includedin the fiber slurry, the aqueous crosslinking solution or can be sprayedor otherwise coated onto the mat later using known techniques.

DETAILED DESCRIPTION OF THE INVENTION

It is known to make reinforcing nonwoven mats from glass fibers and touse these mats as substrates in the manufacture of a large number ofroofing and other products. Any known method of making nonwoven mats canbe used, such as the conventional wet laid processes described in U.S.Pat. Nos. 4,129,674, 4,112,174, 4,681,802, 4,810,576, and 5,484,653, thedisclosures of each being hereby incorporated herein by reference. Inthese processes a slurry of glass fiber is made by adding glass fiber toa typical white water in a pulper to disperse the fiber in the whitewater forming a slurry having a fiber concentration of about 0.2-1.0weight percent, metering the slurry into a flow of white water to dilutethe fiber concentration to about 0.1 wt. percent or below, anddepositing this mixture onto a moving screen forming wire to dewater andform a wet nonwoven fibrous mat. Usually an aqueous binder is thenapplied to the mat such as with a curtain coater and the excess binderis removed by a vacuum knife and the resultant wet mat is dried in anoven which heats the mat to a temperature high enough to cure thebinder. This known process, with modifications as will be described, isused in the present invention. Alternative forming methods for makingthe mat include the use of well known paper or board making processessuch as cylinder forming, etc. and probably even “dry laying” usingcarding or random fiber distribution.

The preferred technique for the making of mats of the present inventionis forming a dilute aqueous slurry of fibers and depositing the slurryonto an inclined moving screen forming wire to dewater the slurry andform a wet nonwoven fibrous mat, on machines like a Hydroformer™manufactured by Voith—Sulzer of Appleton, Wis., or a Deltaformer™manufactured by North County Engineers of Glenns Falls, N.Y.

The slurry used in the above mat forming process contains fibers,preferably glass fibers making up all or most of the fibers, and aNovolac powdered resin, preferably phenolic Novolac. The particle sizeshould be such that most to all of the particles will be entrapped inthe mat during forming and not be migrated or washed out of the mat withthe whitewater or aqueous crosslinking agent as these liquids flowthrough or out of the partially or fully formed mat.

The length and diameter of the glass fibers can be selected based on theintended application and desired properties, but for use in theheadliner laminates disclosed herein, the preferred size of the glassfibers will be one inch long with an average fiber diameter of about 16microns. For headliner mat, at least some fibers longer than one inchmay prove to be better than one inch long. Any type of glass fiber canbe used, but E glass is most plentiful and is preferred for theheadliner application. Generally, the greater the fiber diameter and thelonger length of the fibers, the stiffer will be the resultant mat andvice versa.

It has been found that when the fibers selected for the mat are one inchlong, and about sixteen micron diameter E glass fibers, the preferredparticle size of the Novolac is minus 40 mesh to plus 100 mesh (U.S.Standard screens) or about 149-420 microns. If the particles are muchcoarser than minus 40 mesh, they will tend to form lumps in or on top ofthe mat, and if much finer than plus 100 mesh, insufficient Novolacpowder will remain in the mat. Where shorter or smaller diameter fibersare used in substantial amounts, novolac particles smaller than 149microns can be used and accordingly, where longer or larger diameterfibers are used in substantial amounts, novolac particles larger than149 microns must be used and some particles larger than 420 microns canbe used.

Preferably, for a mat for an automotive headliner product, enoughNovolac particles are added to the whitewater slurry to produce a matcontaining about 45 weight percent Novolac resin in the finished drymat. The preferred phenolic powder is available from Georgia Pacific ofAtlanta, Ga., as 2026 Grade. Mats of the present invention preferablycontain about 10-60 weight percent novolac with about 45-55 wt. percentbeing preferred and about 48-52 wt. percent being most preferred.

Phenolic Novolac resins are described in a book entitled REINHOLDPLASTICS APPLICATIONS SERIES—PHENOLIC RESINS, by David F. Gould,published by Reinhold Publishing Corporation of New York, pages 31-33 asa crosslinking agent starved, insoluble, fusible resin made by usingless than a stoichiometric amount of crosslinking agent in thecondensing step, such as 0.9 mole of formaldehyde per 1 mole of phenolwhere the condensing step takes place in an acidic medium. Novolacresins are well known, are generally quite stable and are thermoplastic,but are generally too brittle to be of practical use and serve almostentirely as intermediates for the production of thermosetting resins.Novolac powders can be white, pink, yellow or tan in color. Propertiesof novolac resin include a melting point of about 85-95 degrees C., freephenol about 8-11 percent, and inclined plate flow of about 15-16millimeters.

Hexamethylene tetramine (HMT) is a known crosslinking, hardening, agentand is preferred, but other known hardening agents can be used. The HMTor other hardening agent is preferably added to the mat as an aqueoussolution in a post addition to a wet web of fibers and novolac resinparticles. Suitable additions of HMT to the mat as the mat enters theoven include about 3-5 wt. percent based on the dry weight of the mat orabout 7-10 wt. percent based on the weight of novolac resin in the mat.Greater amounts of hardening agent can be present, but is unnecessaryand increases the cost of the mat. If less than about 3 percent is used,the novolac will not fully cure to a thermoset resin when the mat ismolded under heat and pressure to form a laminate. The HMT concentrationin the solution can vary greatly, but concentrations of 10, 15 and 25wt. percents have been used successfully.

The wet nonwoven mat of glass fiber is then transferred to a secondmoving screen and run through a saturating station, preferably using aconventional curtain coater, where an aqueous crosslinking agent isapplied to the mat in any one of several known ways. The saturated matis then run over one or more suction knives in a known manner whilestill on the moving screen to remove excess aqueous crosslinking agentsolution. The preferred crosslinking agent for phenolic Novalac ishexamethylene tetramine, but other known crosslinking agents likeparaformaldehyde can also be used.

The wet mat is then transferred to a wire mesh moving oven belt orhoneycomb drum and run through an oven to dry the wet mat and to melt orsubstantially melt the novolac powder sufficiently to flow into andaround the places where the fibers contact and/or cross one another inclose proximity to bond the fibers together in the mat. When usingphenolic novolac powder, such as Georgia Pacific Corporation's GP-2026,the preferred maximum oven temperature is about 149 degrees C. (300degrees F.), but this can be varied some as the time at temperature isvaried to accomplish the disclosed objective. The novolac in thefinished dry mat should be mostly soluble in acetone, indicating a verylow level of crosslinking or cure, but not completely soluble. The mostpreferred novolac solubility of the partially cured resin in the mat inacetone is at least about 70 wt. percent, such as about 85 wt. percent,but can be in the range of about 35 to about 90 or 95 wt. percent. It isvery important that the acetone solubility of the mat be no less thanabout 35, preferably no less than about 50 wt. percent. The lower theacetone solubility, the less flexible the mat for later molding, i.e. iftoo stiff, the mat won't drape or form complex curved shapes properly.

The majority of the fibers are glass fibers and preferably all thefibers are glass fibers. The glass fibers should be at least 0.75 inchlong or longer, more preferably at least one inch long and can be longersuch as about 1.25 or 1.5 inches long or longer. For other uses than usedisclosed in detail herein, the fibers can be shorter than 0.75 inch.The glass fibers can have various fiber diameters dependent on thestrength and other properties desired in the mat as is well known, butsince the mat is intended to be relatively stiff, fibers having adiameter of at least 13 microns are preferred and at least 15 micron ismore preferred, such as M fiber which has an average fiber diameter ofabout 15.5-16.5 microns. It is preferred that the fibers be coated withan amino or ureido silane containing size composition which are wellknown and readily available from fiber glass manufacturers.

It is preferred that the length of the chopped strands of glass fiber besuch that when the chopped strand is added to the wet mat machine in thestock preparation section the fiber does not completely disperse,leaving some multi-fiber bundles in the stock. These bundles, muchsmaller in numbers of fibers and bundle size than the chopped strandused in the prior art as discussed earlier, are beneficial to thestiffness of the present mat product and its stiffening performance whenlaminated to foam. This is accomplished in normal whitewater with afiber length of at least 1 inch and most preferably at least 1.25 inch.The skilled artisan will recognize that this can also be accomplishedwith shorter fiber by modifying the whitewater in known ways to reducedispersion effectiveness, reducing agitation and/or time in the pulperand the stock tank or a combination of these. The preferred fibers are Mor K 137 and K or M 117 E glass fibers available from Johns ManvilleInternational, Inc. of Denver, Co., but most a any commercially wet chopglass fiber product will be suitable. While the majority of the fibersare glass fibers, a minor portion of non-glass fibers can also be used,such as man made or natural organic fibers like Nylon™, polyester,polyethylene, polypropylene, cellulose or cellulose derivatives, etc.

The basis weight of the mat will depend upon the specific application.For stiffening polymeric fibrous webs for use in automotive headliners,the preferred basis weight of the dry mat for molding with a polyesterfiber web to make automotive headliners is about 4.75 pounds per 100square feet with the glass fibers constituting about 2.75 pounds per 100square feet, but basis weights of about 2.25-4 pounds per 100 squarefeet, particularly 2.25-3 pounds per 100 square feet, should also besuitable for this application and basis weights as low as 1.2 lbs. per100 square feet are effective for greatly increasing the strength andmodulus of fiber glass wool boards and foam boards. The basis weight canbe decreased or increased, depending upon the desirable rigidity andstrength in the laminate. Basis weights as low as 0.5 pounds per 100square feet can be rolled up at the end of the mat machine and later cutand handled for use. The maximum weight would be determined by thecapability of the wet mat forming line and/or oven. Typically, for usein making laminates for automotive headliners, the glass fiber contentof the mat is in the range of 40-60 wt. percent, preferably 45-55 wt.percent and most preferably about 50 wt. percent.

The mats of the present invention may be hot molded alone as one or morelayers or hot molded in combination with other materials of all kindssuitable for molding. When the mats of the present invention are used onone or both surfaces of one or more layers of other material and hotmolded, the resulting laminate will have a rigid surface with theremainder of the laminate having the properties of the other material ormaterials used. When the mats of the present invention are used as oneor more interior layers, the interior of the laminate will be rigid andthe surface or surfaces will have the properties of the other materialor materials used.

Hot molding is well known and it is also well known to preheat the matsor laminate precursor sandwich to reduce molding time. When hot moldingmat of the present invention to a three dimensional shape, it ispreferred to first heat the inventive mat layer(s) to a temperaturesufficient to soften or melt the novolac resin in the mat beforedeforming to the desired shape, either in the mold or before enteringthe mold, then molding to the desired shape and further heating to asufficient temperature to react the hardening agent with the novolac tocrosslink and form a thermoset bond in the resin in the mat(s) of thelaminate. When a phenolic novolac is used in the mat a final temperatureof about 193 degrees C. (380 degrees F.) for about 1 minute issatisfactory. Higher final temperatures will shorten the time requiredto reach complete cure, but can darken the novolac color if too high.

EXAMPLE 1

A fiber slurry was prepared by adding one inch long wet M 117 E typeglass wet chopped fiber from Johns Manville International, Inc. ofDenver, Colo., having a silane containing chemical sizing on thesurface, as is well known, to a known cationic white water containingNatrosol™ thickening agent available from Aqualon, Inc. of Wilmington,Del., and a cationic surfactant C-61, an ethoxylated tallow amineavailable from Cytec Industries, Inc. of Morristown, N.J., as adispersing agent to form a fiber concentration of about 0.8 weightpercent. Enough novolac powdered resin, Grade 2026 from Georgia Pacific,was added to the slurry to produce a novolac content in the dry finishedmat of 47.5 wt. percent. After allowing the slurry to agitate for about5 minutes to thoroughly disperse the fibers, the slurry was metered intoa moving stream of the same whitewater to dilute the fiber concentrationto a concentration averaging about 0.05 to 0.006 weight percent beforepumping the diluted slurry to a headbox of a Voith Hydroformer™ where awet nonwoven mat was continuously formed in sufficient basis weight toproduce a dry mat having a basis weight of about 4.4-⅘ pounds per 100square feet.

The wet mat was continuously removed from the forming wire andtransferred to an in-line Sandy Hill Curtain Coater where an aqueoussolution of hexamethylene tetramine was applied in excess and thesaturated mat was then run over a vacuum knife which removed the excessand left a sufficient quantity in the mat to produce a concentration ofhexamethylene tetramine in the dry mat of about 3.5 wt. percent.

The wet mat was then transferred to an oven belt and carried through anoven to dry the mat and to heat the mat to a temperature of about 300degrees F. for about 30 seconds to melt the resin binder, allowing it toflow into and around the fiber crossings to bond the fibers together.

The resultant mat had the following properties.

-   Thickness (mils)-69-   Basis weight (lbs./100 sq. ft.)-4.7-   Tensile Strength-Machine direction (lbs/3 in.)-34-   Cross machine direction (lbs/3 in.)-31-   Novolac solubility in acetone: 85 wt. percent-   Mat emissions on curing at 193 degrees C. for 35 seconds    (micrograms/gram of mat)-   Phenol-69.4 Formaldehyde-18.5 Ammonia-15.4-   Mat emissions on curing at 193 degrees C. for 60 seconds    (micrograms/gram of mat)-   Phenol-80 Formaldehyde-20.1 Ammonia-68.4

This mat was then placed on both sides of a web of dry laid, needledpolyester fibers and this sandwich was then molded at about 193 degreesC. and just enough pressure to deform the sandwich into the shape of thehot mold, and allowed to set under pressure and temperature for oneminute. The resultant molded composite or laminate had a stiffness muchhigher than prior art fiber glass mat and PET fiber laminates and ofchopped strand mat and PET fiber laminates molded in the same manner asabove. Under three point loading according to SAE Method J 949, thestrength of the laminate made with Example 1 mat, as described above,withstood a peak force at failure of 20 Newtons, several Newtons higherthan prior art headliner laminates. The strength of the dry laid andneedled polyester fibers in this test prior to lamination had negligiblestrength that was too low to measure.

EXAMPLE 2

This mat was made in the same manner as the mat in Example 1 except thatthe wet mat, prior to saturation with HMT, contained, on a dry basis, 49wt. percent of the GP 2606 novolac resin particles, and the wet matentering the oven contained about 7 wt. percent HMT, based on the amountof novolac resin, with the remainder being one inch M117 glass fiberavailable from Johns Manville International, of Toledo, Ohio. The basisweight of the dried and partially cured mat was 6.7 lbs/100 sq. ft. Thismat had the following properties:

-   Machine direction tensile strength-60 lbs. per 3 in.-   Cross machine direction tensile-60 lbs. per 3 in.

When this mat was laminated as described in Example 1, the resultantlaminate had a stiffness about 2-3 times that of the prior art resolephenolformaldehyde bonded chopped strand mat and polyester fiber web(described in Example 1) laminate.

EXAMPLES 3-5

These examples show the effect of different drying oven temperatures onthe acetone solubility of the novolac resin in the partially cured mats.These mats were made in the same manner described in Example 1 exceptthat the mat contained 47.5 wt. percent GP 2026 resin and the basisweight of the mats ranged between 4.6 and 4.7 lbs./100 sq. ft. Example 3was dried and treated at 300 degrees F., Example 4 at 325 degrees F. andExample 5 at 350 degrees F., all for about 30 seconds, to produce arange of acetone solubilities in the partially cured mats. Theproperties are shown in the following Table.

TABLE Example 3 Example 4 Example 5 Basis weight 4.6 4.7 4.7 (lbs./100sq. ft.) Thickness (mils) 70 69 73 Machine Tensile (lbs/3 inch) 26 65140 Cross Machine Tensile (lbs/3 inch) 36 50 143 Acetone solubility (%wt. loss) 43.5 33.9 16.7

These mats were molded in the method described in Example 1 and the matof Example 3 was suitable for making laminates of various typesincluding laminates for automotive headliners. However, mats withacetone solubility of less than about 35 wt. percent, based on theweight of the novolac resin in the mat could not be molded since thephenolic formaldehyde (novolac) resin bonding the fibers together wascured too much to flow at high temperatures.

EXAMPLE 6

A mat was made using the procedure described in Example 1 except thatthe novolac resin content was 25 wt. percent and a much lighter weightmat having a basis weight of 1.7 lbs./100 sq. ft. was produced. This matwas then laminated to two faces of a foam board and to a fiber glasswool board producing laminates having the following properties:

Mat/Foam board Mat/FG wool board Peak strength (Newtons) 12.5 67 Modulusof Rupture (MPa) 530 3245

The modulus of rupture of the foam board itself was too low to measure.The strength of the FG wool board alone was 27 newtons and the modulusof rupture of the FG wool board alone was 328 MPa. Thus, even relativelylight weight mats of the present invention produces substantial strengthimprovement to light weight boards.

The mat and laminates of the present invention have further advantagesover the prior art products. These include a substantially lower levelof formaldehyde emissions during molding than when using prior art matsbonded with resole resins like “B” staged phenolic resin and a lowercost compared to mats containing chopped strand to produce acceptablemodulus of failure.

Numerous modifications can be made to the preferred embodiment disclosedin the examples. One can modify the amount of novolac and the basisweight to achieve the desired level of moldability and strength in themolded laminate. Various known pigments, fillers, and other knownadditives can be incorporated into the mat by addition to either thewhitewater or to the aqueous crosslinking solution or slurry for thefunction they are known to provide.

When the word “about” is used herein it is meant that the amount orcondition it modifies can vary some beyond that so long as theadvantages of the invention are realized. Practically, there is rarelythe time or resources available to very precisely determine the limitsof all the parameters of ones invention because to do would require aneffort far greater than can be justified at the time the invention isbeing developed to a commercial reality. The skilled artisan understandsthis and expects that the disclosed results of the invention mightextend, at least somewhat, beyond one or more of the limits disclosed.

Later, having the benefit of the inventors disclosure and understandingthe inventive concept and embodiments disclosed including the best modeknown to the inventor, the inventor and others can, without inventiveeffort, explore beyond the limits disclosed to determine if theinvention is realized beyond those limits and, when embodiments arefound to be without unexpected characteristics, those embodiments arewithin the meaning of the term about as used herein. It is not difficultfor the skilled artisan or others to determine whether such anembodiment is either as might be expected or, because of either a breakin the continuity of results or one or more features that aresignificantly better than reported by the inventor, is surprising andthus an unobvious teaching leading to a further advance in the art.

While the preferred embodiments of the invention have been disclosed indetail, other embodiments within the described invention and havingother functional additives known or obvious to those skilled in the artare considered to be part of the present invention and are intended tobe included in the invention claimed below.

1. A method of making a wet laid nonwoven mat bound with a novolac resincomprising the steps of: a) dispersing fibers and novolac resinparticles in water to form a dilute slurry, b) flowing said slurry ontoa moving first permeable belt to form a wet layer of wet nonwoven fibersand resin particles, c) transferring said wet layer off of saidpermeable belt onto a second moving permeable belt, d) saturating saidwet layer with an aqueous solution or slurry containing a crosslinkingagent and removing excess slurry or solution and excess crosslinkingagent from said wet layer, e) transferring said wet layer off of saidsecond permeable belt onto an oven belt, and f) drying said wet layer toform a dry mat, the improvement comprising that said resin is a novolacpowder having an acetone solubility greater than 95 wt. percent, thatthe aqueous solution or slurry contains a hardening agent for thenovolac, the amount of said resin and hardening agent in the finisheddried mat is at least 10-65 wt. percent, and said novolac resin is incontact with the hardening agent and is cured sufficiently reduce theacetone solubility to between about 35 and about 95 weight percent togive sufficient strength to the mat for handling and further processing,but not so much that the mat looses its ability to conform to a desiredshape and bond to another mat or different material under heat andpressure.
 2. The method of claim 1 wherein the hardening agent ishexamethylene tetramine (HMT).
 3. The method of claim 1 wherein thefibers are glass fibers about one inch long, wherein the glass fibersmake up about 90-40 wt. percent of the mat and said wet layer on theoven belt contains about 7-10 wt. percent of a hardening agent, based onthe weight of novolac particles in said wet layer.
 4. The method ofclaim 3 wherein said finished mat contains about 45-55 wt. percent ofnovolac resin having an acetone solubility of at least 49 wt. percent.5. The method of claim 2 wherein said finished mat contains about 45-55wt. percent of novolac resin having an acetone solubility of at leastabout 49 wt. percent.
 6. A laminate having a core selected from a groupconsisting of foam board, a web of intermingled polymer fibers and afiber glass wool board with two opposed surfaces of the core beingbonded to a mat comprising glass fibers bonded together at the locationswhere the fibers cross each other with up to about 60 weight percent,based on the dry weight of the mat, of novolac resin, said resin havingan acetone solubility of at least 35 wt. percent, and at least about 3weight percent hardening agent for said resin based on the weight of themat, said hardening agent amounting to at least 7 weight percent of theweight of the novolac resin, said novolac resin being substantially inmelted form bonding the fibers together.
 7. The laminate of claim 6wherein the hardening agent is hexamethylene tetramine (HMT).
 8. Thelaminate of claim 6 wherein the glass fibers in the mat are about oneinch long and wherein the glass fibers make up about 90-40 wt. percentof the mat and the novolac resin makes up at least 10 wt. percent of themat.
 9. The mat laminate of claim 6 wherein said mat contains about45-55 wt. percent of novolac resin having a particle size of about minus40 mesh and plus 100 mesh and the acetone solubility of the resin binderis at least about 70 wt. percent.
 10. The laminate of claim 7 whereinsaid mat contains about 45-55 wt. percent of novolac resin having aparticle size of about minus 40 mesh and plus 100 mesh and the acetonesolubility of the resin binder is at least about 70 wt. percent.
 11. Thelaminate of claim 8 wherein said mat contains about 45-55 wt. percent ofnovolac resin having a particle size of about minus 40 mesh and plus 100mesh and the acetone solubility of the resin binder is at least about 70wt.
 12. The laminate described in claim 10 wherein the core is a web ofintermingled polymer fibers.
 13. The laminate described in claim 10wherein the core is a fiber glass wool board.
 14. The laminate describedin claim 10 wherein the core is a foam product.